High pressure structural and vibrational properties of the spin-gap system Cu2PO4(OH)

J Phys Condens Matter. 2013 Jan 30;25(4):045402. doi: 10.1088/0953-8984/25/4/045402. Epub 2012 Dec 20.

Abstract

The structural and vibrational properties of the spin-gapped system Cu(2)PO(4)(OH) have been investigated at room temperature under high pressure up to ~20 GPa by Raman scattering and synchrotron-based x-ray diffraction and infrared (IR) spectroscopic measurements. The orthorhombic phase (space group Pnnm, z = 4) remains stable up to at least 7 GPa where it undergoes a weakly first order structural transition (with negligible volume drop) to a monoclinic phase (space group P2(1)/n, z = 4) with an abrupt monoclinic distortion. Refinement of atomic positions has been performed for the low pressure phase. The conspicuous changes in the vibrational spectra (Raman as well as far-IR) confirm this phase transition. At further higher pressures the monoclinic angle increases rapidly and the system transforms irreversibly into a disordered phase. Detailed vibrational analyses have been performed in the orthorhombic phase and pressure-induced structural evolution has been correlated with the vibrational modes corresponding to the Cu-O bonds. A strong negative pressure dependence of hydroxyl mode frequencies (as observed from the mid-IR absorption spectra) supports the pressure-induced structural disordering at higher pressures.

Publication types

  • Research Support, Non-U.S. Gov't